TWI680143B - Method to produce functionalized, low viscosity ethylene-based polymers - Google Patents

Abstract

The invention provides a method for forming a "functionalized and ethylene-based polymer" from a polymer mainly composed of ethylene and at least one polar compound. The method comprises heat-treating a composition in at least one extruder. Forming a polymer melt, the composition comprising the ethylene-based polymer, the at least one polar compound, and at least one peroxide, the extruder comprising at least one barrel; and wherein the at least one The maximum barrel temperature of the peroxide in the at least one extruder has a half life, which is less than 1/4 of the minimum residence time of the polymer melt in the at least one extruder.

The invention further provides a composition comprising at least the following: a) a polymer based on ethylene, which contains a melt viscosity of less than 50.000 cP at 350 ° F (177 ° C), and b) at least one peroxide It contains a half-life period from 0.10 to 2.00 minutes at a temperature from 160 ° C to 190 ° C.

Description

Method for making functionalized, low viscosity, ethylene-based polymers References for related applications

This application claims the benefit of US Provisional Application No. 61 / 922,003, filed on December 30, 2013, which is hereby incorporated by reference.

The present invention relates to a method for making functionalized, low viscosity, ethylene-based polymers.

background

During reactive extrusion, compared to polymers with higher molecular weight and higher viscosity, polymers with lower molecular weight, lower viscosity and predominantly ethylene have lower melting temperatures due to less viscous energy dissipation. Therefore, a long extruder is required to increase the melting temperature to induce the grafting of the peroxide.

80 L/D)。此可使用二個串列擠壓機(例如，每一者係40 L/D)達成。於低熔融溫度，典型環氧化物具有對於一標準反應性擠壓方法係太長的半生期。因此，需要一大量部份之擠壓機長度使低黏度聚合物加熱至過氧化物可分解及誘發自 由基可觀地接枝至聚合物上之溫度。但是，問題於此等經接枝之聚合物粒化時產生。於接枝發生之溫度(對於典型過氧化物係>200℃)，低黏度的經接枝之聚合物具有極低熔融強度，且不能於水面下粒化。因此，需要一大量之擠壓機長度使經接枝之聚合物熔融物冷卻至用於粒化之足夠低的溫度。經接枝之聚合物及/或擠壓方法係於下列參考案中描述：WO 2007/146875及WO 2006/039774。但是，仍需要對於低分子量並以乙烯為主之聚合物之新的接枝方法。此等需求已藉由下列發明滿足。 Grafting low-molecular weight ethylene-based polymers currently requires a high ratio of length to diameter (L / D) of the extruder (> 60 L / D, and is preferably

80 L / D). This can be achieved using two tandem extruders (for example, each of which is 40 L / D). At low melting temperatures, typical epoxides have half-life periods that are too long for a standard reactive extrusion process. Therefore, a large portion of the extruder length is required to heat the low viscosity polymer to a temperature at which the peroxide can decompose and induce considerable grafting of free radicals onto the polymer. However, problems arise when these grafted polymers are pelletized. At the temperature at which the grafting occurs (> 200 ° C for typical peroxide systems), the grafted polymer with low viscosity has extremely low melt strength and cannot be pelletized under water. Therefore, a large amount of extruder length is required to cool the grafted polymer melt to a temperature sufficiently low for pelletization. The grafted polymers and / or extrusion methods are described in the following references: WO 2007/146875 and WO 2006/039774. However, there is still a need for new grafting methods for low molecular weight, ethylene-based polymers. These needs have been met by the following inventions.

Summary of invention

The invention provides a method for forming a "functionalized and ethylene-based polymer" from a polymer mainly composed of ethylene and at least a polar compound. The method comprises heat treating a composition in at least one extruder. Forming a polymer melt, the composition comprising the ethylene-based polymer, the at least one polar compound, and at least one peroxide, the extruder comprising at least one barrel; and wherein the at least one The maximum barrel temperature of the peroxide in the at least one extruder has a half life, which is less than 1/4 of the minimum residence time of the polymer melt in the at least one extruder.

The invention also provides a composition comprising at least the following: a) an ethylene-based polymer containing a melt viscosity of less than 50.000 cP at 350 ° F (177 ° C), and b) at least one peroxide, which is contained in a half-life period at a temperature from 160 ° C to 190 ° C from 0.10 to 2.00 minutes.

Figure 1 depicts the amount of MAH grafts of the present invention as a function of peroxide type and flow rate at high barrel temperatures (defined in Tables 2A and 2B).

Figure 2 depicts the amount of MAH grafts of the present invention as a function of peroxide type and flow rate at low barrel temperature (defined in Tables 2C and 2D).

Figure 3 depicts the residual peroxide as a function of peroxide type and flow rate at low barrel temperature (defined in Tables 2C and 2D).

Detailed description

The process of the present invention has been found to provide improved granulation of functionalized and ethylene-based polymers formed from low viscosity and ethylene-based polymers. It was also found that the functionalization reaction of low-viscosity, ethylene-based polymers can occur at lower temperatures, and therefore, less polymer melt cooling is required for subsurface pelletization. It has also been found that the method of the invention uses a shorter L / D extruder to provide a sufficient degree of functionalization.

As discussed above, the present invention provides a method for forming a "functionalized and ethylene-based polymer" from an ethylene-based polymer and at least one polar compound, the method comprising subjecting a composition to at least one Heat treatment in an extruder to form a polymer melt, the composition comprising the ethylene-based polymer, the at least one polar compound, and at least one peroxide, the extruder comprising at least one barrel; and The maximum barrel temperature of the at least one peroxide in the at least one extruder has a half-life period, which is less than 1/4 of the minimum residence time of the polymer melt in the at least one extruder.

A method of the invention may include a combination of two or more embodiments described herein.

In one embodiment, the peroxide has a half-life of the maximum barrel temperature of the at least one extruder, which is less than 1/5 of the minimum residence time of the polymer melt in the at least one extruder. And further less than 1/6 of the minimum residence time.

In one embodiment, the extruder includes at least two barrel sections.

In one embodiment, the extruder includes at least two barrel sections in a modular extruder.

In one embodiment, the peroxide is decomposed into at least one primary radical selected from the following radicals: a) RCOO ^. Wherein, R is an alkyl group, and further is a C1-C6 alkyl group; b) RO ^. Wherein, R a group-based, and further a line C1-C6 alkyl; or c) ROC (O) ^O. Wherein, R is a monoalkyl group, and further is a C1-C6 alkyl group.

In one embodiment, the peroxide is decomposed into one or more primary radicals (Z‧), and the energy of each radical is greater than or equal to 100 kcal / mole.

Larger energy differences between free radicals and hydrogen on the polymer to be extracted are preferred. See P.R. Dluzneski, "Peroxide Curing of Elastomers", Rubber Chemistry and Technology, Volume 74, page 452.

In one embodiment, ethylene-based polymers have less than 50,000 cP, further the melt viscosity of less than 40,000 cP at 350 ° F (177 ° C).

In one embodiment, the peroxide has a SADT of less than or equal to 80 ° C, further less than or equal to 75 ° C, and further less than or equal to 70 ° C. SADT refers to a pure peroxide (peroxide with a purity of> 90% by weight).

In one embodiment, the pure peroxide has a SADT that is greater than or equal to 50 ° C, further greater than or equal to 55 ° C, and furthermore greater than or equal to 60 ° C.

In one embodiment, the pure peroxide has a SADT (purity> 90% by weight) of SADT from 55 ° C to 90 ° C, and further from 55 ° C to 80 ° C.

In one embodiment, the pure peroxide has a temperature range from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, from 0.10 to 2.00 minutes, further from 0.10 to 1.00 minutes, and further from 0.10 to 0.50 minutes. period.

In one embodiment, the peroxide has a half-life period of from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, less than 30 seconds, further less than 25 seconds, and further less than 20 seconds.

In one embodiment, the peroxide has a half-life period from 160 ° C to 200 ° C, further from 170 ° C to 195 ° C, less than 30 seconds, further less than 25 seconds, and further less than 20 seconds.

In one embodiment, the peroxide has a temperature from 160 ° C to 190 ° C, and further from 170 ° C to 190 ° C, which has a temperature of less than 20 seconds, further At 15 seconds, it is a half-life of less than 10 seconds. In one embodiment, the temperature of the polymer melt is from 160 ° C to 190 ° C, and further from 170 ° C to 190 ° C.

In one embodiment, the peroxide has a half-life period from 160 ° C. to 200 ° C., further from 170 ° C. to 195 ° C., less than 20 seconds, further less than 15 seconds, and further less than 10 seconds. In one embodiment, the temperature of the polymer melt is from 160 ° C to 200 ° C, and further from 170 ° C to 195 ° C.

In one embodiment, the peroxide has a temperature from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, has a temperature of from 1 second to less than 30 seconds, further from 1 second to less than 25 seconds, and further from 1 second. Less than half a life of 20 seconds.

In one embodiment, the peroxide has a temperature from 160 ° C to 200 ° C, further from 170 ° C to 195 ° C, and has a temperature of from 1 second to less than 30 seconds, further from 1 second to less than 25 seconds, and further from 1 second. Less than half a life of 20 seconds.

In one embodiment, the peroxide has a temperature from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, and has a temperature from 1 second to 20 seconds, further from 1 second to 15 seconds, and further from 1 second. Less than half a life of 10 seconds.

In one embodiment, the peroxide has a temperature from 160 ° C to 200 ° C, further from 170 ° C to 195 ° C, and has a temperature of from 1 second to less than 30 seconds, further from 1 second to less than 25 seconds, and further from 1 second. Less than half a life of 20 seconds.

Suitable peroxides include, without limitation, TRIGONOX 131 (third pentyl peroxy 2-ethylhexyl carbonate, CAS # 70833-40-6); TRIGONOX 117; and TRIGONOX 42S (third butyl peroxy- 3,5,5 trimethylhexanoate, CAS # 13122-18-4).

A peroxide may include a combination of two or more of the described embodiments.

In one embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and the α-olefin is a C ₃ -C ₂₀ α-olefin, and further a C ₃ -C ₁₀ α- Olefin.

In one embodiment, the at least one polar compound is an anhydride-containing compound (for example, maleic anhydride) and / or a carboxylic acid-containing compound (for example, maleic acid). In a further embodiment, the composition further comprises a ketone. In a further embodiment, the weight ratio of the polar compound to the ketone is from 0.80 to 1.20, further from 0.90 to 1.20, and further from 1.00 to 1.20.

The invention also provides a composition comprising at least the following: a) a polymer based on ethylene, which contains a melt viscosity of less than 50.000 cP at 350 ° F (177 ° C), and b) at least one peroxide The substance has a half-life period of from 0.10 to 2.00 minutes at a temperature of from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C.

A composition of the invention may comprise a combination of two or more embodiments as described herein.

In one embodiment, the peroxide is decomposed into at least one primary radical selected from the following radicals: a) RCOO ^. Wherein, R is an alkyl group, and further is a C1-C6 alkyl group; b) RO ^. Wherein, R a group-based, and further a line C1-C6 alkyl; or c) ROC (O) ^O. Wherein, R is a monoalkyl group, and further is a C1-C6 alkyl group.

In one embodiment, the peroxide is decomposed into one or more primary radicals (Z‧), and the energy of each radical is greater than or equal to 100 kcal / mole.

In one embodiment, ethylene-based polymers have a melt viscosity of less than 40,000 cP, and further less than 30,000 cP at 350 ° F (177 ° C).

In one embodiment, the peroxide has a SADT of less than or equal to 80 ° C, further less than or equal to 75 ° C, and further less than or equal to 70 ° C. SADT means pure peroxide (peroxide with purity> 90% by weight).

In one embodiment, the pure peroxide has a SADT that is greater than or equal to 50 ° C, further greater than or equal to 55 ° C, and furthermore greater than or equal to 60 ° C.

In one embodiment, the pure peroxide has a SADT (purity> 90% by weight) of SADT from 55 ° C to 90 ° C, and further from 55 ° C to 80 ° C.

In one embodiment, the pure peroxide has a temperature from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, and has a temperature from 0.10 to 2.00 minutes, further from 0.10 to 1.00 minutes, and further from 0.10 to 0.50 minutes. Half-life.

In one embodiment, the peroxide has a temperature from 160 ° C to 190 ° C, and further from 170 ° C to 190 ° C, has a temperature of less than 30 seconds, further At 25 seconds, it is a half-life of less than 20 seconds.

In one embodiment, the peroxide has a half-life period of less than 15 seconds at a temperature from 160 ° C to 190 ° C, further from 170 ° C to 190 ° C, and further less than 10 seconds.

In one embodiment, the temperature of the polymer melt is from 160 ° C to 190 ° C, and further from 170 ° C to 190 ° C.

Suitable peroxides include, without limitation, TRIGONOX 131 (third pentylperoxy-2-ethylhexyl carbonate, CAS # 70833-40-6); TRIGONOX 117; and TRIGONOX 42S (third butyl peroxide) Oxy 3,5,5 trimethylhexanoate, CAS # 13122-18-4).

A peroxide may comprise a combination of two or more of the described embodiments.

In one embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and the α-olefin is a C ₃ -C ₂₀ α-olefin, and further a C ₃ -C ₁₀ α- Olefin.

In one embodiment, the composition further includes a polar compound. In a further embodiment, the at least one polar compound is an anhydride-containing compound (for example, maleic anhydride) and / or a carboxylic acid-containing compound (for example, maleic acid). In a further embodiment, the composition further comprises a ketone. In a further embodiment, the weight ratio of the polar compound to the ketone is from 0.80 to 1.20, further from 0.90 to 1.20, and further from 1.00 to 1.20.

The invention also provides an article comprising at least one component formed from a composition of the invention.

In one embodiment, the object is selected from a film, a fiber, a foam, a molded part, a coating, an adhesive, or a dispersion.

In one embodiment, the object is selected from an automobile component, an adhesive, a computer component, a roof material, a structural material, a carpet component, or a shoe component.

Polar compounds

The term "polar compound" as used herein refers to an organic compound containing at least one heteroatom (e.g., O, N, S, P).

Examples of polar compounds include, without limitation, ethylene unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride ; Vinyl benzyl halides such as vinyl benzyl chloride and vinyl benzyl bromide; alkyl acrylates and alkyl methacrylates such as methyl acrylate, ethyl acrylate, Butyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and dodecyl methacrylate; and ethylene unsaturated alkylene oxides, such as acrylic ring Oxypropyl ester, glycidyl methacrylate, and glycidyl ethacrylate. Preferred ethylene unsaturated amine-reactive compounds include maleic anhydride, acrylic acid, methacrylic acid, propylene acrylate, and propylene methacrylate, and the maleic anhydride system is more preferable. See also US Patent No. 7,897,689 (columns 51 to 54).

In one embodiment, the polar compound is a carbonyl-containing compound selected from the group consisting of maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, and dimaleate ( Octadecane) ester, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, nadic anhydride, methylnadic anhydride, alkenyl succinic anhydride, Maleic acid Acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid, their esters, their imines, their salts, and their Diels -Alder).

In one embodiment, the polar compound is a compound containing an anhydride and / or a carboxylic acid. In a further embodiment, the polar compound is maleic anhydride. In a further embodiment, the composition further comprises a ketone. In a further embodiment, the weight ratio of the polar compound to the ketone is from 0.80 to 1.20, further from 0.90 to 1.20, and further from 1.00 to 1.20.

In one embodiment, the polar compound is monosilane, and further is a vinyltrialkoxysilane, for example, vinyltrimethoxysilane or vinyltriethoxysilane.

In one embodiment, the polar compound has a molecular weight of from 50 to 500 g / mole, further from 80 to 400 g / mole, and further from 100 to 300 g / mole.

A polar compound may comprise a combination of two or more embodiments as described herein.

extrusion

Examples of extruders include, without limitation, twin-screw extruders co-rotating and co-rotating, counter-rotating twin-screw extruders, tangential twin-screw extruders, Buss Kokneader extruders, planetary extruders , And single screw extruder. Specific examples include twin-screw extruders that rotate intermeshing in the same direction. Furthermore, the features of interest are design specifications-length / diameter (L / D ratio), mixing section (screw design). Typically, for a single extruder, the maximum L / D ratio may be about 60. For longer L / D ratios, the two extruders are coupled. screw The lever design includes, without limitation, mixing elements including, for example, kneading discs, left-handed spiral elements, turbine mixing elements, gear mixing elements, and the like, and combinations thereof.

In one embodiment, the L / D ratio of the extruder is from 36 to 80 L / D.

In one embodiment, the temperature of the polymer melt is from 130 ° C to 220 ° C. In one embodiment, the temperature of the polymer melt is from 130 ° C to 190 ° C, and further from 130 ° C to 180 ° C.

In one embodiment, a cooling device, such as a melt cooler, is attached to the extruder to reduce the temperature of the polymer melt.

In one embodiment, a devolatization device is attached to the extruder to remove residual reactants.

In one embodiment, based on a functionalized and ethylene-based polymer, the functionalized and ethylene-based polymer contains from 0.01 to 3.00% by weight, further from 0.02 to 2.50% by weight, further From 0.03 to 2.00% by weight of grafted polar compounds. In another embodiment, the functionalized and ethylene-based polymer is an ethylene-based polymer grafted with maleic anhydride.

Modern extruders (modules and single barrels) have the ability to control the temperature across different sections. Therefore, different barrel temperatures can be set and controlled along the barrel length. The maximum barrel temperature is the highest set temperature. Different barrel temperatures are desired to control the temperature of the polymer pellets and the melt along the length of the extruder.

The extruder barrel contains the screw or rotor of the extruder. They are used to hold the polymer in the extruder and are designed to be heated and cooled The channels provide heating or cooling of the polymer to be processed. They are designed to withstand the high temperatures and pressures encountered during extrusion operations.

Functionalized and ethylene-based polymers

The term "functionalized and ethylene-based polymer" as used herein means that it contains at least one chemical group (chemical substituent) connected by a covalent bond and this group contains at least one heteroatom Polymer based on ethylene. A heteroatom system is defined as an atom that is not carbon or hydrogen. Generally heteroatoms include, without limitation, oxygen, nitrogen, sulfur, and phosphorus.

Some examples of compounds that can be grafted onto ethylene-based polymers include ethylene unsaturated carboxylic acids and acid derivatives such as esters, anhydrides, and acid salts. Examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, tetrahydrophthalic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, nadic anhydride , Humic acid, and mixtures thereof. Maleic anhydride is a preferred compound.

、酐，及此等之組合；且其中，R係氫或烷基，R’係氫或烷基。於一另外實施例，每一烷基基團獨立地係甲基、乙基、丙基，或丁基。於一實施例，經官能化並以乙烯為主之聚合物係選自一經官能化之乙烯均聚物或一經官能化之乙烯/α-烯烴異種共聚物。於一另外實施例，經官能化並以乙烯為主之聚合物係一經官能化之乙烯均聚物。於另一實施例，經官能化並以乙烯為主之聚合物係一經官 能化之乙烯/α-烯烴異種共聚物，且進一步係一經官能化之乙烯/α-烯烴共聚物。較佳之α-烯烴包含C3-C8 α-烯烴類，且進一步係丙烯、1-丁烯、1-己烯，及1-辛烯。 In one embodiment, the functionalized and ethylene-based polymer includes at least one functional group selected from the following:

, Anhydride, and combinations thereof; and wherein R is hydrogen or alkyl and R ′ is hydrogen or alkyl. In a further embodiment, each alkyl group is independently methyl, ethyl, propyl, or butyl. In one embodiment, the functionalized and ethylene-based polymer is selected from a functionalized ethylene homopolymer or a functionalized ethylene / α -olefin heteropolymer. In a further embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene homopolymer. In another embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene / α -olefin heteropolymer, and further is a functionalized ethylene / α -olefin copolymer. Preferred α -olefins include C3-C8 α -olefins, and are further propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer includes an anhydride; and further, maleic anhydride. In one embodiment, the functionalized and ethylene-based polymer is selected from a functionalized ethylene homopolymer or a functionalized ethylene / α -olefin heteropolymer. In a further embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene homopolymer. In another embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene / α -olefin heteropolymer, and further is a functionalized ethylene / α -olefin copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer is a polymer grafted with maleic anhydride. In one embodiment, the functionalized and ethylene-based polymer is selected from a functionalized ethylene homopolymer or a functionalized ethylene / α -olefin heteropolymer. In another embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene homopolymer. In another embodiment, the functionalized and ethylene-based polymer is a functionalized ethylene / α -olefin heteropolymer, and further is a functionalized ethylene / α -olefin copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has less than or equal to 40,000 cP at 350 ° F (177 ° C), further less than or equal to 30,000 cP, further less than or equal to 20,000 cP, and Further, it has a melt viscosity of less than or equal to 15,000 cP. In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. . Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a temperature greater than or equal to 2,000 cP at 350 ° F (177 ° C), further greater than or equal to 3,000 cP, further greater than or equal to 4,000 cP, and further greater than Or equal to 5,000 cP melt viscosity. In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has from 2,000 cP to 50,000 cP, further from 3,000 cP to 40,000 cP, and further from 4,000 cP to 30,000 cP at 350 ° F (177 ° C), and It further has a melt viscosity from 5,000 cP to 20,000 cP. In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In an embodiment, the functionalized and ethylene-based polymer has a molecular weight of less than or equal to 5.0, further less than or equal to 4.0, further less than or equal to 3.5, and further a molecular weight less than or equal to 3.2. Distribution (Mw / Mn). In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a molecular weight distribution (Mw / Mn) of less than or equal to 3.0, further less than or equal to 2.9, and further less than or equal to 2.8. In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a molecular weight distribution (Mw / Mn) greater than or equal to 1.1, further greater than or equal to 1.3, and further greater than or equal to 1.5. In another embodiment, the functionalized and ethylene-based polymer is a carboxylic acid and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the carboxylic acid and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. . Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a molecular weight distribution (Mw / Mn) greater than or equal to 2.0, further greater than or equal to 2.2, and further greater than or equal to 2.5. In another embodiment, the functionalized and ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized and ethylene-based polymer. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a weight average of greater than or equal to 2000 g / mole, further greater than or equal to 3000 g / mole, and further greater than or equal to 4000 g / mole. Molecular weight (Mw). In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has less than or equal to 60,000 g / mole, further less than or equal to 50,000 g / mole, and further less than or equal to 40,000 g / mole. Weight average molecular weight (Mw). In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a melting greater than or equal to 300 g / 10 minutes, further greater than or equal to 400 g / 10 minutes, and further a melting greater than or equal to 500 g / 10 minutes. Index (I2) or calculated melting index (I2). In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has less than or equal to 1500 g / 10 minutes, further less than or equal to 1200 g / 10 minutes, and further less than or equal to 1000 g / min. 10 minute melt index (I2) or calculated melt index (I2). In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has 40% or less, further less than or equal to 35%, further less than or equal to 30%, further less than or equal to 25%, Furthermore, it is a percentage crystallinity of less than or equal to 20%, which is determined by DSC. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In an embodiment, the functionalized and ethylene-based polymer has a percentage crystallinity of greater than or equal to 2%, further greater than or equal to 5%, and further greater than or equal to 10%, which is determined by DSC . In another embodiment, the polymer that is functionalized with anhydride and / or carboxylic acid and is mainly ethylene is an ethylene / α-olefin heteropolymer that is functionalized with anhydride and / or carboxylic acid, and further is a copolymer . Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a density greater than or equal to 0.850 g / cc, further greater than or equal to 0.855 g / cc, and further greater than or equal to 0.860 g / cc. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and are further propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, the functionalized and ethylene-based polymer has a density of less than or equal to 0.900 g / cc, further less than or equal to 0.895 g / cc, and further less than or equal to 0.890 g / cc. . In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

In one embodiment, and functionalized ethylene-based polymer having from of 0.855g / cm ³ to 0.900g / cm ^3, further lines from 0.860g / cm ³ to 0.895g / cm ^3, and further lines from 0.865 g / cm ³ to 0.890g / cm ³ of density. In another embodiment, the anhydride- and / or carboxylic acid-functionalized ethylene-based polymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin heteropolymer, and is further a copolymer. Preferred α -olefins include C3-C8 α -olefins, and further are propylene, 1-butene, 1-hexene, and 1-octene.

Once functionalized and predominantly ethylene-based polymers may comprise a combination of two or more embodiments as described herein.

A functionalized ethylene / α-olefin hetero-copolymer may comprise a combination of two or more embodiments as described herein.

A functionalized ethylene / α-olefin copolymer may comprise a combination of two or more embodiments as described herein.

Polymers based on ethylene for functionalization

Suitable ethylene-based polymers include, for example, high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), uniformly branched linear ethylene polymers, and uniformly branched essence It is a linear ethylene polymer (which is an ethylene-based polymer with uniformly branched long chain branches).

In a preferred embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and is further an ethylene / α-olefin copolymer.

Suitable alpha-olefins include, without limitation, C3-C20 alpha-olefins, and It is further a C3-C10 α-olefin. More preferred α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, and further include propylene, 1-butene, 1-hexene. , And 1-octene, and further 1-butene and 1-octene.

In one embodiment, the ethylene-based polymer has a melt viscosity of less than or equal to 50,000 cP at 350 ° F (177 ° C), further less than or equal to 40,000 cP, and further less than or equal to 30,000 cP. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a melt viscosity at 350 ° F (177 ° C) of 2,000 cP or more, 4,000 cP or more, and 5,000 cP or more. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a melt viscosity at 350 ° F (177 ° C) from 2,000 cP to 20,000 cP, further from 4,000 cP to 16,000 cP, and further from 5,000 cP to 10,000 cP. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has less than or equal to 3.5, and further less than or equal to 3.0, and further less than or equal to Molecular weight distribution (Mw / Mn) at 2.7. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a molecular weight distribution from 1.1 to 3.5, and further from 1.1 to 3.0, and further from 1.1 to 2.7. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and is further an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In an embodiment, the ethylene-based polymer has a melting index (I2 or greater than 500 g / 10 minutes), further greater than or equal to 800 g / 10 minutes, and further greater than or equal to 1000 g / 10 minutes. MI), or calculated melt index (I2). In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a melting of less than or equal to 2000 g / 10 minutes, further less than or equal to 1800 g / 10 minutes, and still more less than or equal to 1600 g / 10 minutes of melting. Index (I2 or MI), or calculated melting index (I2). In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a percent crystallinity of less than or equal to 40%, further less than or equal to 30%, and further less than or equal to 20%, which is determined by DSC. In another embodiment, an ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further The step is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In an embodiment, the ethylene-based polymer has a percentage crystallinity of 2% or more, further 5% or more, and 10% or more, which is determined by DSC. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a percentage crystallinity from 2 to 30%, further from 5 to 25%, and further from 10 to 20%, which is determined by DSC. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a percentage crystallinity from 10 to 27%, further from 15 to 25%, and further from 18 to 23%, which is determined by DSC. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the polymer based on ethylene has a density of 0.855 g / cc or more, further 0.860 g / cc or more, and a density of 0.865 g / cc (1cc = 1cm ³ ) or more. . In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a density of less than or equal to 0.900 g / cc, further less than or equal to 0.895 g / cc, and still more preferably less than or equal to 0.890 g / cc. In another embodiment, it is mainly ethylene The polymer is an ethylene / α-olefin heteropolymer, and is further an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a thickness from 0.855 g / cc to 0.900 g / cc, and further from 0.860 g / cc to 0.895 g / cc, and further from 0.865 g / cc to 0.890 g. / cc density. In another embodiment, the ethylene-based polymer has an ethylene / α-olefin heteropolymer, and is further an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer has a thickness from 0.870 g / cc to 0.885 g / cc, and further from 0.872 g / cc to 0.882 g / cc, and further from 0.875 g / cc to 0.880 g / cc density. In another embodiment, the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and further is an ethylene / α-olefin copolymer. Suitable α-olefins are as described above.

Some examples of ethylene / α-olefin copolymers include suitable AFFINITY GA polyolefin plastomers available from The Dow Chemical Company and Clariant suitable LICOCENE performance polymers. Other examples of ethylene / α-olefin polymers suitable for the present invention include the ultra-low molecular weight ethylene polymers described in U.S. Patent Nos. 6,335,410, 6,054,544, and 6,723,810, each of which is incorporated herein For reference.

In one embodiment, the ethylene-based polymer is a uniformly branched linear ethylene / α-olefin heteropolymer, and further is a copolymer, or a uniformly branched substantially linear ethylene / α-olefin heteropolymer, and It is further a copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer is a homogeneously branched linear ethylene / α-olefin heteropolymer, and is further a copolymer. Suitable α-olefins are as described above.

In one embodiment, the ethylene-based polymer is a homogeneously branched substantially linear ethylene / α-olefin heteropolymer, and is further a copolymer. Suitable α-olefins are as described above.

The terms "homogeneous" and "homogeneous branching" are used to refer to a system in which an alpha-olefin co-monomer system is randomly distributed within a particular polymer molecule and all such polymer molecules have the same or substantially the same comonomer pair Ethylene is one of the ethylene / α-olefin heteropolymers.

Uniformly branched linear ethylene heteropolymers lack long-chain branches but do have short-chain branches (which are derived from comonomers polymerized in heterogeneous copolymers) and are evenly distributed within the same polymer chain and among different polymers Ethylene polymer between chains. These ethylene / α-olefin heteropolymers have a linear polymer backbone, no measurable long chain branches, and a narrow molecular weight distribution. These types of polymers are disclosed, for example, in US Pat. No. 3,645,992 to Elston, and subsequent methods of manufacturing these polymers using a double metallocene catalyst have been developed, for example, in EP 0 129 368; EP 0 260 999; U.S. Patent No. 4,701,432; U.S. Patent No. 4,937,301; U.S. Patent No. 4,935,397; U.S. Patent No. 5,055,438; and WO 90/07526, each of which is incorporated herein For reference. As discussed, homogeneously branched linear ethylene heteropolymers lack long chain branches, as is the case with linear low density polyethylene polymers or linear high density polyethylene polymers. Uniformly branched linear ethylene / α-olefin copolymer Commercial examples include TAFMER polymers from Mitsui Chemical Company, and EXACT and EXCEED polymers from ExxonMobil Chemical Company.

Uniformly branched substantially linear ethylene / α-olefin heteropolymers are described in U.S. Patent Nos. 5,272,236; 5,278,272; 6,054,544; 6,335,410 and 6,723,810, each of which is incorporated herein by reference. Substantially linear ethylene / α-olefin heteropolymers and copolymers have long chain branches. The long chain branches have the same comonomer distribution as the polymer backbone and may have approximately the same length as the length of the polymer backbone. "Substantially linear" typically refers to a polymer that is distributed on average from "0.01 long chain branches per 1,000 carbon systems" to "3 long chain branches per 1000 carbon systems." The length of a long chain branch is longer than the carbon length of a short chain branch formed from the incorporation of a comonomer into the polymer backbone.

Some polymers can have 0.01 long-chain branches per 1,000 total carbons to 3 long-chain branches per 1,000 total carbons, further from 0.01 long-chain branches per 1,000 total carbons to 1,000 per thousand total carbons. 2 long-chain branches, and further distributed from 0.01 long-chain branches per 1,000 total carbons to 1 long-chain branch per 1,000 total carbons.

The substantially linear ethylene / α-olefin heteropolymers and copolymers form a unique kind of uniformly branched ethylene polymer. These are essentially different from the conventional homogeneous branched linear ethylene / α-olefin heteropolymers of the known kind discussed above, and further, they are not equivalent to the traditional non-uniform "Ziegler- Natta) catalyst polymerization "linear ethylene polymers (e.g., ultra-low density polyethylene (ULDPE), linear low density polyethylene (LLDPE), or High-density polyethylene (HDPE), for example, made using the technology disclosed by Anderson et al. In U.S. Patent No. 4,076,698); it is also not a highly branched polyethylene with high pressure and free radical initiation (For example, low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymer, and ethylene vinyl acetate (EVA) copolymer) are the same kind.

The uniformly branched substantially linear ethylene / α-olefin heteropolymers and copolymers that can be used in the present invention have excellent processability, even if they have a relatively narrow molecular weight distribution. Surprisingly, the melt flow ratio (I10 / I2) according to ASTM D 1238 of the substantially linear ethylene heteropolymer can vary widely and is substantially independent of the molecular weight distribution (Mw / Mn or MWD). This surprising behavior is with traditional homogeneously branched linear ethylene heteropolymers (such as, for example, described by Elston in US 3,645,992) and heterogeneously branched conventional "polyethylene via Ziegler-Natta" linear heteropolymers Things such as, for example, those described in US 4,076,698 to Anderson et al. Unlike substantially linear ethylene heteropolymers, linear ethylene heteropolymers (whether homogeneous or heterogeneous branches) have rheological properties such that as the molecular weight distribution increases, the I10 / I2 value also increases.

The long-chain branch can be determined using 13C nuclear magnetic resonance (NMR) spectroscopy, and can be quantified using the method of Randall (Rev. Macromol. Chem. Phys., C29 (2 & 3), 1989, p. 285-297). It is hereby incorporated by reference. Two other methods are gel permeation chromatography combined with a low-angle laser light scattering detector (GPCLALLS) and gel permeation chromatography combined with a differential viscometer detector (GPC-DV). The use of these techniques for long-chain branch detection, as well as the basic theory, are well documented in the literature. E.g, See Zimm, BH and Stockmayer, WH, J. Chem. Phys., 17,1301 (1949), and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112 .

In contrast to "substantially linear ethylene heteropolymer or copolymer", "linear ethylene heteropolymer or copolymer" means that the polymer lacks a measurable or cocoatable long-chain branch, i.e., the polymer is 1000 carbons are distributed with less than 0.01 long chain branches.

An ethylene-based polymer may comprise a combination of two or more embodiments as described herein.

An ethylene / α-olefin heteropolymer may comprise a combination of two or more embodiments as described herein.

An ethylene / α-olefin copolymer may comprise a combination of two or more embodiments as described herein.

additive

A composition of the invention may include one or more additives. Additives include, without limitation, stabilizers, colorants, nucleating agents, fillers, lubricants, flame retardants, and plasticizers.

Typically, the polymers and polymer compositions used in the present invention are treated with one or more stabilizers, for example, antioxidants such as IRGANOX 1010 and IRGAFOS 168, both of which are now provided by BASF. Polymers are typically treated with one or more stabilizers prior to extrusion or other melting methods.

In one embodiment, the composition further includes an olefin-based polymer. In another embodiment, the olefin-based polymer is selected from the group consisting of a polyethylene homopolymer, an ethylene-based heteropolymer, a polypropylene homopolymer, and a propylene-based heteropolymer. Or a hydrogenated homopolymer or copolymer of butadiene or other material having two alkenyl groups per monomer.

In another embodiment, the composition further includes a polar polymer. In another embodiment, the polar polymer is selected from the group consisting of polyesters, polyamines, polyethers, polyetherimines, polyvinyl alcohols, polylactic acids, polyurethanes, and polycarbonates. Type, polyurethane, or polyvinyl chloride. In another embodiment, a functionalized, ethylene-based polymer system is dispersed in a polar polymer to form its particles.

The composition of the present invention may include a combination of two or more embodiments described herein.

In one embodiment, the functionalized and ethylene-based polymer is further reacted with a primary or secondary diamine and / or alcohol amine. Primary-secondary diamines include, without limitation, N-ethylethylenediamine, N-phenylethylenediamine, N-phenyl-1,2-phenylenediamine, N-phenyl-1,4- Phenylenediamine, and N- (2-hydroxyethyl) -ethylenediamine. Alcoholamines include without limitation 2-aminoethanol, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 2- (2-amine Ethoxy) -ethanol, and 2-aminobenzyl alcohol.

application

The invention also provides an object comprising at least one component formed from a composition of the invention.

In one embodiment, the object is selected from a film, a fiber, a foam, a molded part, a coating, an adhesive, or a dispersion.

In one embodiment, the object is selected from an automobile component, an adhesive, a computer component, a roof material, a structural material, a carpet component, or a shoe component.

In one embodiment, the object is a carpet, an adhesive, a wire sheath, a cable, a coating, a fiber, or a foam. In another embodiment, the object is a connection layer between extruded sheet, film or profile; a connection layer between cast sheet, film or profile; an automobile skin; a canopy; a A tarpaulin; a roof structure; a steering wheel; a powder coating; a powder condensation module; a consumer durable; a computer component; a strip; or a shoe component.

Functionalized, ethylene-based polymer compositions can be used in a variety of applications, including without limitation adhesives for polymer substrates and foams, such as adhesives for polyurethane films and foams , And polyester adhesives; dyes, paint adhesives, and paint adhesion promoters; welding applications; automotive interior and exterior; lubricants and engine oil components; fibers; fabrics; paper or corrugated packaging, polymer composition Compatibilizers; toughening agents for polymer compositions; conveyor belts; films; adhesives; shoe components; artificial leather; injection molded objects such as injection molded toys; roofing and structural materials; dispersions; carpet components such as, Carpet substrates; and artificial turf. Further applications include adhesives, tie layers of multilayer films, and blends with other polar polymers for impact modification.

definition

Unless stated to the contrary, all test methods are as of the filing date of this disclosure.

The term "heat treatment" as used herein refers to applying heat to a material or composition. Heat can be applied, for example, through different types of electric heating devices, through oil or water jacketed sleeves, or through heat dissipation in a mechanical mixer.

The term "composition" as used herein includes a mixture of materials that includes the composition, reaction products and decomposition products formed with the materials from the composition.

The term "polymer" as used herein refers to a polymer compound prepared by polymerizing monomers of the same or different types. The generic term polymer therefore includes the term homopolymer (used to refer to polymers prepared from only one type of monomer, and it is important to understand that trace amounts of impurities can be incorporated into the polymer structure), and the term heterogeneous copolymer as defined below . Trace amounts of impurities, such as catalyst residues, can be incorporated into the polymer and / or into it.

The term "heterogeneous copolymer" as used herein refers to a polymer prepared by polymerizing at least two different monomers. The generic term heterogeneous copolymer therefore includes copolymers (used to refer to polymers prepared from two different monomers), and polymers prepared from more than two different types of monomers.

The term "olefin-based polymer" as used herein refers to containing a large amount of olefin monomers in a polymerized form, such as ethylene or propylene (based on the weight of the polymer), and optionally may include A polymer of one or more comonomers.

The term "ethylene-based polymer" as used herein means that it contains a large amount of ethylene monomer (based on polymer weight) in a polymerized form and optionally includes one of one or more comonomers polymer.

The term "ethylene / α-olefin heteropolymer" as used herein refers to a heteropolymer comprising a large amount of ethylene monomer (based on the weight of the heteropolymer) in a polymerized form and at least one alpha-olefin .

The term "ethylene / α-olefin copolymer" as used herein means that it contains a large amount of ethylene monomer (based on the weight of the copolymer) in a polymerized form and an α-olefin as the only two monomer forms Of a copolymer.

The term "bond dissociation energy" (BDE) as used herein refers to the strength of a chemical bond. It is defined by a single bond by standard enthalpy change during uniform cleavage, and the reactants and products of the uniform cleavage reaction are at 298K. See Blanksby S.J. and Ellison G.B., Acc. Chem. Res. 2003, 36, 255-263. The stability and reactivity of free radicals generated by the hydrogen BDE reaction and hydrogen atoms.

The term "primary radical group" as used herein refers to a radical that is decomposed from a peroxide and formed before any secondary reactions such as beta decomposition, decarboxylation, etc. occur.

The terms "comprising", "including", "having" and their derivatives are not intended to exclude the existence of any additional components, steps or procedures, whether or not they are explicitly disclosed. To avoid any doubt, unless stated to the contrary, all compositions requested through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymers or otherwise. In contrast, the term "consisting essentially of" excludes any other component, step or procedure from any scope described thereafter, except to the extent that it is not important for operability. The term "consisting of" excludes any component, step or procedure that is not explicitly described or listed.

Test Methods Half life

The half-life value is obtained by measuring the decomposition of a peroxide solution in a solvent. The half-life period can be calculated from the following Arrhenius equation: k _d = A‧e ^{-Ea / RT} , where A is the Arrhenius frequency factor, E _a is the activation energy, T is the test temperature, and R is the ideal gas constant. For example, see Table A below. The half-life (t _1/2 ) is calculated from the following equation: t _1/2 = ln2 / k _d . The value of "A" and the value of "Ea" can each be determined from the literature (for example, the literature of Arkema).

The data for this work were obtained from the Arkema document "Arkema Peroxide Half-Life Calculator", 2005 Arkema, Inc., which is available via "www.arkema-inc.com/pdf/HalfLife.xls", which is used in 0.2M peroxide in dodecane (solvent).

SADT (Self-Accelerated Decomposition Temperature)

The SADT value of a peroxide can be determined as follows. The packaging containing this peroxide is placed in an oven equilibrated at the test temperature. The time when the packaged peroxide reached 2 ° C below the expected test temperature was recorded. The oven is maintained at a fixed test temperature for up to 1 week, or until it exceeds the control phenomenon.

If the packaged peroxide does not exceed the test (oven) temperature of 6 ° C within one week, the peroxide is "passed." If the packaged peroxide exceeds the test temperature by 6 ° C within one week, the peroxide is "failed".

This test is repeated in 5 ° C increments until the test fails. The failure temperature was reported as SADT for this peroxide. SADT depends on three main factors: 1) the structure of the peroxide; 2) the peroxide is diluted with mineral essential oil, mineral oil or other diluent; and 3) the size of the package. Preferably, pure peroxide (> 90% by weight of peroxide) is tested. In general, SADT determines the maximum package size. The largest package is determined by UN shipping classification and regulations. See, for example, Sanchez et al., "Peroxides and Compounds (Organic)", Encyclopedia of Chemical Technology, Volume 18, 1996. Each of TRIGONOX 117 AND TRIGINOX 101 is classified as UN 3105, and SADT is measured in a 110-pound package. TRIGONOX 29 is classified as UN 3101, and SADT is measured in a 55-pound package. See also AkzoNobel's product brochure, "Starters and Reactor Additives for Thermoplastics", 2010.

Melt viscosity

Melt viscosity is measured according to ASTM D 3236 (177 ° C, 350 ° F) using a Brookfield Digital Viscometer (Model DV-III, 3rd Edition), and a disposable aluminum sample chamber. The spindle used is generally a SC-31 hot-melt spindle, which is suitable for measuring viscosities ranging from 10 to 100,000 centipoise. The sample is poured into the sample chamber, which in turn is inserted into a Brookfield Thermosel and locked in place. The sample chamber has a groove at the bottom, which is installed at the bottom of the Brookfield Thermosel to ensure that the sample chamber does not rotate when the spindle is inserted and rotated. The sample (about 8-10 grams of resin) is heated to the desired temperature until the molten sample is about 1 inch below the top of the sample chamber. The viscometer device is lowered and the spindle is trapped in the sample chamber. Continue to decrease to the viscosity meter The brackets are aligned with Thermosel. Turn on the viscometer and start operating at a shear rate. This results in torque readings in the range of 40 to 60% of the total torque capability, which is based on the rpm output of the viscometer. The reading is obtained for about 15 minutes per minute, or until the value is stable, at this time, the final reading is recorded.

Melt Index

The melt index (I2, or MI) of polymers based on ethylene is measured according to ASTM D-1238, conditions 190 ° C / 2.16 kg. For polymers with a high I2 (I2 is greater than or equal to 200 g / mole, the melt index is preferably calculated from Brookfield viscosity as described in US Patent Nos. 6,335,410; 6,054,544; 6,723,810. I2 (190 ° C / 2.16 kg) = 3.6126 [10 ^{(log (} η ^{) -6.6928) /-1.1363} ] -9.3185, where η = melt viscosity at 350 ° F, cP.

Gel permeation chromatography

The average molecular weight and molecular weight distribution of ethylene-based polymers are determined by a chromatography system, which consists of a Polymer Laboratories model PL-210 or a Polymer Laboratories model PL-220. The column and rotating rack cell are operated at 140 ° C for polymers based on ethylene. The column was three Polymer Laboratories 10-micron, mixed-B columns. The solvent is 1,2,4-trichlorobenzene. The sample was prepared at a concentration of "0.1 g polymer" in a "50 ml" solvent. The solvent used to prepare the sample contained "200 ppm of butylated hydroxybenzene (BHT)". The sample was slightly heated at 160 ° C. Prepared by stirring for 2 hours. The injection volume is "100 microliters" and the flow rate is 1.0 ml / min. The calibration of the GPC column set is performed with a narrow molecular weight distribution polystyrene standard purchased from Polymer Laboratories (UK) The polystyrene standard peak molecular weight is converted into polyethylene using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6,621 (1968)): M _polyethylene = A x (M _polystyrene ) ^B , where M is a molecular weight, A has a value of 0.4315, and B is equal to 1.0.

The calculation of polyethylene equivalent molecular weight was performed using VISCOTEK TriSEC software version 3.0. The molecular weight of polypropylene-based polymers can be determined using the Mark-Houwink ratio according to ASTM D6474.9714-1, where for polystyrene, a = 0.702 and log K = -3.9, and for polypropylene, a = 0.725 and log K = -3.721. For polypropylene-based samples, the column and rotary rack compartments are operated at 160 ° C.

Differential scanning calorimetry

Differential scanning calorimetry (DSC) is used to measure the crystallinity in samples mainly made of polyethylene (PE) and samples mainly made of polypropylene (PP). Approximately 5 to 8 mg of the sample is weighed and placed in a DSC pan. The lid is rolled onto the pan to ensure a closed atmosphere. The sample was placed in a DSC box, and then heated at a rate of about 10 ° C / minute for a temperature of 180 ° C for PE (230 ° C for PP). The sample was held at this temperature for 3 minutes. Then, the sample was cooled at a rate of 10 ° C / minute, to -60 ° C for the PE system (-40 ° C for the PP system), and maintained at this temperature for 3 minutes. The sample was then heated at a rate of 10 ° C / minute to complete melting (second heating). Percent crystallinity is calculated by dividing the heat of fusion (H _f ) determined from the second curve by the theoretical heat of fusion, 292 J / g for PE systems (165 J / g for PP systems), and multiplying the quantity by 100. Calculations (eg, for PE,% crystallinity = (H _f / 292 J / g) x 100; and for PP,% crystallinity = (H _f / 165 J / g) x 100).

Unless stated otherwise, the melting point (T _m ) of each polymer is determined from the second heating curve obtained by DSC as described above. The crystallization temperature (T _c ) is measured from the first cooling curve.

density

Samples for density measurement were prepared according to ASTM D 1928. The polymer sample was pressed at 190 ° C and 30,000 psi (207 MPa) for 3 minutes and then at 21 ° C and 30,000 psi (207 MPa) for 1 minute. Measurements were made within 1 hour of sample compression using ASTM D792, Method B.

Fourier transform infrared spectroscopy (FTIR) analysis-maleic anhydride content

The concentration of maleic anhydride is determined by the ratio of the peak height of maleic anhydride at a wave number of 1791 cm ^-1 to the polymer reference peak (in the case of polyethylene, the wave number is 2019 cm ^-1 ). The maleic anhydride content is calculated by multiplying this ratio by an appropriate correction constant. The equation (with reference peak for polyethylene) for polyolefins grafted via Malay has the following pattern as shown in Equation 1.

MAH (% by weight) = A * ([FTIR peak area at 1791 cm-1] / [FTIR peak area 2019 cm-1] + B * [FTIR peak area at 1712 cm-1] / [at 2019 cm- FTIR peak area of 1)) (Equation 1)

The correction constant A can be determined using a C13 NMR standard. Actual calibration constants will vary slightly, depending on the instrument and polymer. The second component at wave number 1712 cm ^-1 illustrates the presence of maleic acid, which is negligible for newly grafted materials. However, over time, maleic anhydride is easily converted to maleic acid in the presence of water. Depending on the surface area, significant hydrolysis can occur over several days under ambient conditions. The acid has a clear peak at a wave number of 1712 cm ^-1 . The constant B in Equation 1 is the correction of the difference in extinction constant between the anhydride and the acid group.

The sample preparation process begins in a heated press and produces a compact between two protective films, typically with a thickness of 0.05 to 0.15 mm, which is at 150-180 ° C for 1 hour. MYLAR and TEFLON are suitable protective films to protect the sample from the pressure plate. It is not necessary to use aluminum foil (maleic anhydride reacts with aluminum). The pressure plate needs to be under pressure (~ 10 tons) for about 5 minutes. The sample was cooled to room temperature, placed in a suitable sample holder, and then scanned by FTIR. Background scanning needs to be performed before sample scanning or when needed. The test accuracy is good, with an inherent deviation of less than ± 5%. Samples should be stored in desiccant to avoid excessive hydrolysis. The water content in the product is measured up to 0.1% by weight. However, the conversion of anhydride to acid can be temperature reversed, but it can take up to 1 week for complete conversion. This conversion is best performed in a vacuum oven at 150 ° C; a good vacuum (close to 30 inches of Hg) is required. If the vacuum is less than appropriate, the sample is susceptible to oxidation, resulting in an infrared peak at about 1740 cm ^-1 , which will make the value of the graft amount too low. Maleic anhydride and maleic acid are individually represented by peaks of approximately 1791 and 1712 cm ^-1 .

The polymers, compositions and methods of the present invention and the use thereof are explained more fully with the following examples. The following examples are provided for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.

experiment

The materials used in this study and their properties are shown in Tables 1A and 1B.

Table 1C below shows the half-life of the three peroxides at different temperatures. According to experience, it takes 5-6 half-lives for more than 99% of peroxides to decompose into free radicals to initiate grafting. In a typical reactive extrusion process, it is desirable to have a residence time on the order of less than 1 minute to avoid unreasonably low production rates. Therefore, desirably tied to the melting of grafting The temperature has a half life of about 10 seconds. In this case, the melting temperature is 170 ° C-190 ° C.

As seen in Table 1B, "lower half-life" peroxides typically also have lower SADT (Self-Accelerated Decomposition Temperature) values. If the SADT is reduced to values close to room temperature, special storage and transportation requirements are required to avoid safety hazards associated with low SADT values. Therefore, the choice of peroxide is determined by half-life and safe handling requirements.

Graft reaction

The grafting experiment was completed on a Coperion 25mm twin screw reaction extrusion line with 48L / D. With 12 barrels and 9 temperature zones. Based on the weight of the solution, maleic anhydride is dissolved in methyl ethyl ketone (MEK) solvent with 50% by weight of maleic anhydride. Maleic anhydride was added to MEK in a flask and stirred overnight with a magnetic stir bar. A mixture of MEK solvent, maleic anhydride, and peroxide was injected into barrel # 4 (zone # 3) of the extruder. Liquid pump The system is an ISCO D1000 positive displacement pump. Unreacted peroxides and volatile compounds are removed via a "gas-liquid separator" at one of the devo ports in barrel # 10 (zone # 8). A Sterling liquid ring vacuum pump (model LEMC 60) provides a negative pressure of "20 Hg" to assist in the removal of volatiles.

The polymer pellets were measured in the throat of the extruder using a K-tron model KCLKT20 twin-screw weightless feeder. The feed rate was varied from 12.5 to 37.5 pounds per hour and at a fixed 500 rpm screw speed. Tables 2A-2D show typical conditions used during this test operation.

Measure minimum residence time

The residence time in an extruder is by using a pulse method to introduce a color mark at time 0, and by observing the reaction (color change) as a function of time when the extruder discharges measuring. The minimum residence time in the extruder is measured as the time between the introduction of a tracking particle and the time when the color is first observed at the die exit.

A dense color masterbatch additive having the same base resin as the system (composition) of interest is selected. For this study, one of AMPACET's dark red polyethylene thick masterbatches was selected. The base resin ensures that the pigment in the concentration masterbatch will be compatible with the resin system in the extruder.

The extrusion system begins with standard operating conditions that are desirable for the measurement. This method is performed for several minutes until the system reaches steady state operation. For a twin-screw extruder, 3-5 concentrated color masterbatch pellets are dropped into the feed port of the extruder. Once the concentrated masterbatch pellets are introduced into the system, a stopwatch is activated. This is the measurement start time. The strands of material leaving the mold were observed. Stop the stopwatch as soon as the first perceivable color is present at the die exit. This time indicates Minimum residence time after extruder system. Three measurements were taken and the average was recorded.

Calculate average residence time

The average residence time was calculated using a commercial "AKRO-CO-TWIN SCREW, 3rd Edition" software. The calculation of average residence time using AKRO-CO software is based on the paper "A Composite Model for Solid Conveying, Melting, Pressure and Fill Factor Profiles in Modular Co-rotating Twin Screw Extruders" by S. Bawiskar & JLWhite, International Polymer Processing , Section XII ( 4), 1997, pages 331-340.

The average residence time of this method = the total filling volume of the extrusion / the total volume flow rate of the polymer. The calculation of the extruder volume can be determined by the method described in the document "Geometry of Fully Wiped Twin Screw Equipment", Polymer Engineering and Science , Volume 18, Issue 12, pages 973-984, September 1978, which is used in Booy ML . The fill volume is calculated based on the flow characteristics of the individual spiral elements of the screw design. Volume flow rate is based on feed rate and melt density. The processing results are shown in Tables 2A-2D below.

** Weight percentage based on weight of functionalized and ethylene-based polymer

*** milligrams of residual peroxide per gram of functionalized and ethylene-based polymer

The results of the first group of maleic anhydride graft experiments are shown in Tables 2A, 2B, and Figure 1. TRIGONOX 101 is used in the example in Table 2A. In Table 2B, the examples (1-4 to 1-9) were each prepared with another peroxide, TRIGONOX 29 or TRIGONOX 117.

As seen in Table 2A, at the same "maximum barrel temperature", the amount of MAH grafting decreased for Comparative Examples 1-2 and 1-3, and the amount of residual peroxide increased. As can be seen in Table 2B, maleic anhydride does graft on all examples 1-4 to 1-9, but, on the example using a "lower temperature" peroxide, TRIGONOX 117, (1-7 to 1-9 ) To reach a higher grafting amount of maleic anhydride.

These experiments confirm that at equal mass flow rates, not all peroxides with shorter half-life are effective in grafting maleic anhydride monomers to the polymer backbone. At the same mass flow rate, compared with the composition containing other peroxides, the additional peroxide TRIGONOX 117 has a higher reaction efficiency for grafting maleic anhydride to the basic polymer.

Compared with TRIGONOX 117, one of the "shorter half-life peroxides", TRIGONOX 29, showed a lower grafting amount in the flow velocity range studied. This implies that an increase in the amount of grafting requires a shorter half-life and free radicals with sufficient energy to separate hydrogen from the polymer chain and generate a free radical on the polymer that will be grafted onto the maleic anhydride monomer. Body of the vinyl group.

Tables 2-C and 2-D show experiments using lower barrel temperatures and using Trigonox 101 and Trigonox 117, respectively. The effect of the peroxide type on conversion is illustrated in Figures 2 and 3 at different flow rates. At the same concentration, the sample containing TRIGONOX 117 peroxide had a higher graft content of maleic anhydride than the corresponding sample manufactured with TRIGONOX 101.

TRIGONOX 117 samples were also performed at a higher weight percentage (0.23% by weight) to account for the number of free radicals formed per mole of peroxide. From the active basis, the "TRIGONOX 117" sample of "0.23% by weight" has the same amount of free radicals as the "TRIGONOX 101" sample of "0.15% by weight". At a rate of 10 lb / r, the TRIGONOX 117 sample has a "triple amount" of grafted maleic anhydride. This data confirms that another peroxide, TRIGONOX 117, provides higher grafting efficiency.

One additional reaction variable that demonstrates the higher reactivity of peroxides is the measurement of the amount of unreacted peroxide present in the final cured sample. Figure 3 shows the results of two peroxide types as a function of flow rate. At higher flow rates and lower residence times, the residual peroxide content of each TRIGONOX 101 sample is always significantly higher than the corresponding TRIGONOX 117 sample. This result shows that a larger proportion of the peroxide from TRIGONOX 117 decomposes during the residence time of the reactive extrusion process and can therefore be used to initiate polymer grafting.

In summary, the other peroxide (TRIGONOX 117) consistently provides a higher degree of reaction efficiency with a shorter residence time (higher mass flow rate). This provides a means to increase the grafting rate at lower temperatures or higher mass flow rates.

Claims (12)

A method of forming a "functionalized and ethylene-based polymer" from an ethylene-based polymer and at least one polar compound, the method comprising heat-treating a composition in at least one extruder to form A polymer melt, the composition comprising the ethylene-based polymer, the at least one polar compound, and at least one peroxide; the extruder includes at least one barrel; the polymer melt has from 30 Minimum residence time to 81 seconds; wherein the functionalized ethylene-based polymer comprises from 0.01 to 3.00 wt% of a polar compound and from 0.15 to 0.23 wt% of a peroxide; and wherein the at least one pass half of green oxide having from 0.10 to 2.00 minutes to a temperature of from 190 to 160 ℃ deg.] C, the decomposition of the peroxide and at least a ROC (O) O ^- of the primary radicals, wherein, R a group-based. The method of claim 1, wherein the peroxide has a half life at the maximum barrel temperature of the at least one extruder, which is less than the minimum retention of the polymer melt in the at least one extruder. 1/5 of the time. The method of claim 1 or 2, wherein the ethylene-based polymer has a melt viscosity of less than 50,000 cP at 177 ° C. The method of claim 1 or 2, wherein the peroxide has a SADT (Self-Accelerated Decomposition Temperature) from 55 ° C to 80 ° C based on the pure peroxide. The method of claim 1 or 2, wherein the temperature of the polymer melt is from 160 ° C to 190 ° C. The method according to claim 1 or 2, wherein the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and wherein the α-olefin is a C ₃ -C ₂₀ α-olefin. The method of claim 1 or 2, wherein the at least one polar compound is an anhydride and / or carboxylic acid-containing compound. A composition containing an ethylene-based polymer comprising at least the following: a) an ethylene-based polymer containing a melt viscosity of less than 50,000 cP at 177 ° C, and b) at least one peroxide It contains a half-life period from 0.10 to 2.00 minutes at a temperature from 160 ° C to 190 ° C. The peroxide is decomposed into at least one ROC (O) O ^- primary radical, wherein R is an alkyl group. The composition of claim 8, wherein the ethylene-based polymer is an ethylene / α-olefin heteropolymer, and wherein the α-olefin is a C ₃ -C ₂₀ α-olefin. The composition of claim 8 or 9, further comprising at least one polar compound. The composition of claim 10, wherein the at least one polar compound is an anhydride and / or carboxylic acid-containing compound. A composition as claimed in claim 8 which is used to form a component of an article.